Method for resourceful treatment of gasification furnace slag and petrochemical hazardous waste and microcrystalline glass

Abstract

The present application relates to solid waste treatment technical field, disclose a kind of gasification furnace slag and petrochemical hazardous waste's resource processing method and microcrystalline glass, the method includes the following steps: (1) gasification furnace slag is carried out magnetic separation under effective average magnetic field intensity is 8000~14000G, obtain low magnetic furnace slag;(2) petrochemical hazardous waste incineration ash, low magnetic furnace slag and silicon-containing auxiliary material are mixed, the obtained mixture is carried out high-temperature melting under oxidizing atmosphere, quenching cooling, obtain glass body, again crushing grinding, forming, heat treatment, obtain microcrystalline glass.The present application uses petrochemical hazardous waste incineration ash, gasification furnace slag and silicon-containing auxiliary material as raw material, and microcrystalline glass with high added value is prepared, realizes petrochemical hazardous waste incineration ash and gasification furnace slag harmless, reduction and resource utilization.

Description

Technical Field

[0001] This invention relates to the field of solid waste treatment technology, specifically to a method for the resource-based treatment of gasification slag and petrochemical hazardous waste, and microcrystalline glass. Background Technology

[0002] According to the National Hazardous Waste List (2021 Edition), incineration residue generated in the environmental remediation industry is classified as hazardous waste (HW18). This means that bottom ash and fly ash generated from the incineration and pyrolysis of organic hazardous waste produced in the petrochemical process are still considered hazardous waste and must be included in the management of hazardous waste.

[0003] The widespread use of gasifiers in the petrochemical industry provides industrial fuel gas for production, serves as feedstock for chemical synthesis and fuel oil synthesis, and is also an important source of hydrogen. However, while providing convenience, it also generates a large amount of solid waste: gasifier slag.

[0004] Melt solidification technology utilizes heat to melt solid waste into a glassy substance at high temperatures. The dense crystalline structure of the glass ensures the stability of the solidified form. After vitrification, organic pollutants in solid waste are destroyed or converted into gases through pyrolysis, while radioactive elements and heavy metals are firmly bound within the solidified glass. Currently, solid waste is often converted into glass to achieve volume reduction and harmlessness.

[0005] Patent application CN202110712553.X discloses a method for the high-temperature melting and harmless treatment of waste fly ash coupled with incineration power generation. The method involves uniformly mixing waste fly ash obtained from waste incineration with carbonaceous materials and a binder, then extruding the resulting mixture (with a unit calorific value > 2500 kcal / kg) into a mold. The molded mixture is then added to a high-temperature melting gasification furnace and treated at 1400–1600°C to obtain high-temperature fuel gas and high-temperature slag. The high-temperature slag is then rapidly cooled to obtain a vitreous substance. However, this method uses a gasification melting temperature of 1400–1600°C, which is relatively high and leads to high energy consumption; the added value of the vitreous substance obtained from the resource-based treatment of waste fly ash is low; the added carbonaceous materials have certain requirements regarding calorific value; and the treatment target of this method is waste incineration fly ash.

[0006] Patent application CN201710335453.3 discloses a resource-based clean treatment process for waste fly ash and metallurgical dust. This process co-processes waste fly ash and metallurgical dust, achieving resource utilization and clean disposal of these materials through the rational design of processes and technical parameters such as drying, high-temperature roasting, cooling, flue gas circulation, baghouse dust collection, and flue gas desulfurization. However, the added value of the products generated by this process is low, and the treated materials are waste incineration fly ash and metallurgical dust.

[0007] Patent application CN201510392541.8 discloses a method for treating heavy metals and dioxins in waste-to-energy plant ash and medical incineration ash. This method uses waste-to-energy plant ash, medical incineration ash, and raw coal as raw materials, incinerating them at 1400–1600℃ for detoxification, followed by fly ash remelting and finally water quenching and solidification to obtain a vitreous substance. This method enables the recycling of waste residue, achieving positive economic benefits and environmental protection. However, this method still contains raw coal as raw material, and the amount of raw coal used is too large (90–97%), resulting in low utilization rate of the waste residue; the added value of the vitreous substance generated from the harmless treatment is low; and the treated materials are waste-to-energy plant ash and medical incineration ash.

[0008] Based on the existing technologies mentioned above, current methods for treating solid waste are costly, produce low added value of the waste products, and have not yet been studied for types of solid waste such as petrochemical hazardous waste incineration ash and gasification slag. Summary of the Invention

[0009] To address the shortcomings of existing technologies, this invention provides a method for the resource-based treatment of gasification slag and petrochemical hazardous waste, as well as microcrystalline glass. The microcrystalline glass generated by this method has high added value and excellent performance, achieving the harmlessness, resource utilization, and volume reduction of gasification slag and petrochemical hazardous waste, while also being low in cost.

[0010] To achieve the above objectives, the present invention provides a method for the resource-based treatment of gasification slag and petrochemical hazardous waste, the method comprising the following steps:

[0011] (1) The gasification slag is magnetically separated under an effective average magnetic field strength of 8000-14000G to obtain low magnetic slag.

[0012] (2) The petrochemical hazardous waste incineration ash, the low magnetic furnace slag and silicon-containing auxiliary materials are mixed, and the resulting mixture is melted at high temperature in an oxidizing atmosphere, then quenched and cooled to obtain a glass body, which is then crushed, ground, shaped and heat-treated to obtain microcrystalline glass.

[0013] In the mixture, based on the total weight of the mixture, the content of SiO2 is 45-60 wt%, the content of Na2O is 12-19 wt%, the content of K2O is 0.5-5 wt%, the content of CaO is 4.5-10 wt%, the content of Al2O3 is 5.5-9.5 wt%, the content of Fe2O3 is 3.0-5.1 wt%, and the content of Cr2O3 is 0-0.58 wt%.

[0014] Preferably, in step (1), the gasification slag is subjected to three-stage separation, with the effective average magnetic field strength of the first-stage separation being 8000-9000G, the effective average magnetic field strength of the second-stage separation being 11000-12000G, and the effective average magnetic field strength of the third-stage separation being 12000-14000G.

[0015] Preferably, the average particle size of the low-magnetic furnace slag is less than 1 mm.

[0016] Preferably, in step (1), the gasification slag is selected from at least one of the waste slag discharged after quenching from Texaco gasifiers, Shell gasifiers, and Orient gasifiers.

[0017] Preferably, in step (2), the silicon-containing auxiliary material is selected from at least one of silicon dioxide, quartz sand and waste glass, preferably waste glass.

[0018] The average particle size of the silicon-containing auxiliary material is less than 1 mm.

[0019] Preferably, the preparation process of the petrochemical hazardous waste incineration ash includes: mixing fly ash and bottom ash generated from the incineration of organic petrochemical hazardous waste, and crushing and sieving the resulting premixed ash.

[0020] Preferably, the average particle size of the petrochemical hazardous waste incineration ash is less than 1 mm.

[0021] Preferably, the pH of the leachate from the petrochemical hazardous waste incineration ash is 9-13.

[0022] Preferably, the obtained premixed ash residue is first subjected to impurity removal, then crushed and sieved, wherein the impurity removal step includes: the obtained premixed ash residue is subjected to three-stage countercurrent washing with alkaline solution.

[0023] Preferably, the alkaline solution is selected from saturated sodium carbonate solution and / or saturated sodium bicarbonate solution.

[0024] Preferably, the weight ratio of the alkaline solution to the mixed ash residue is 1:4 to 10.

[0025] Preferably, the operating temperature of the impurity removal step is 40–60°C.

[0026] Preferably, the washing is performed 2 to 3 times, and each washing session lasts 5 to 10 minutes.

[0027] Preferably, the petrochemical hazardous waste incineration ash residue contains, based on the total weight of the petrochemical hazardous waste incineration ash residue, 0.5-2 wt% SiO2, 45-60 wt% Na2O, 0-3.5 wt% Al2O3, 2-4 wt% total Fe2O3, and 0.2-0.6 wt% CaO.

[0028] Preferably, the hazardous characteristics of the petrochemical hazardous waste incineration ash residue are as follows, based on the total weight of the petrochemical hazardous waste incineration ash residue: lead content <20mg / kg, mercury content <5mg / kg, arsenic content <50mg / kg, selenium content <30mg / kg, antimony content <10mg / kg, titanium content <800mg / kg, manganese content <500mg / kg, cobalt content <50mg / kg, barium content <800mg / kg, vanadium content <4000mg / kg, copper content <100mg / kg, zinc content <2500mg / kg, chromium content <4200mg / kg, nickel content <500mg / kg, cadmium content <5mg / kg, and cyanide content <5mg / kg.

[0029] Preferably, in step (2), the weight ratio of the petrochemical hazardous waste incineration ash, low magnetic furnace slag and silicon-containing auxiliary material is 100:110-150:80-150, wherein the silicon-containing auxiliary material is calculated by weight of SiO2.

[0030] Preferably, in step (2), the high-temperature melting step has a melting temperature of 1300-1400℃ and a melting time of 60-90min.

[0031] Preferably, the oxygen content in the oxidizing atmosphere is 8-15%.

[0032] Preferably, in step (2), the kiln ash collected in the high-temperature flue gas generated during the high-temperature melting process is recovered and used to prepare petrochemical hazardous waste incineration ash.

[0033] Preferably, in step (2), the specific process of the heat treatment includes: first heating to 600-650℃ and holding for 30-60 minutes, and then heating to 850-900℃ and holding for 1-2 hours.

[0034] Preferably, the heating rate for the first heating is 6–8 °C / min;

[0035] Preferably, the heating rate of the second heating is 5 to 10 °C / min.

[0036] A second aspect of the present invention provides a microcrystalline glass, which is prepared by the method described above.

[0037] The advantages and beneficial effects of this invention are:

[0038] 1. The method provided by this invention produces microcrystalline glass using petrochemical hazardous waste incineration ash, gasification furnace slag, and silicon-containing auxiliary materials as raw materials. This microcrystalline glass meets the requirements of the "Technical Requirements for Vitrification Products of Solid Waste" (GB / T 41015-2021) standard for "limits on the content of harmful substances in water leaching and acid leaching of vitrification products," thus achieving the harmless treatment of petrochemical hazardous waste incineration ash. At the same time, this microcrystalline glass meets the requirements of the "JCT 872-2019 Microcrystalline Glass for Building Decoration" standard, has high added value, and realizes the resource utilization of petrochemical hazardous waste incineration ash and gasification furnace slag.

[0039] 2. The resource recovery method provided by the present invention removes some of the highly magnetic slag containing iron, cobalt, nickel oxides and their alloys by magnetic separation of gasification slag, thereby removing some of the metallic impurities that are detrimental to the performance of glass-ceramics. At the same time, it is easy to prepare a mixture that meets the composition requirements, so that the resulting glass-ceramics have excellent performance.

[0040] 3. The method provided by this invention can make full use of the existing elements in petrochemical hazardous waste incineration ash and gasification furnace slag, and can produce microcrystalline glass without adding nucleating agents and alkaline substances, thus reducing the use of auxiliary materials and making the cost lower.

[0041] 4. This invention uses an oxidizing atmosphere, eliminating the need for external coal supply; the added gasification slag and silicon-containing auxiliary materials have no specific requirements on calorific value, and are available from a wider range of sources with lower costs. Attached Figure Description

[0042] Figure 1 This is a schematic flowchart of an embodiment of the resource utilization treatment method for gasification slag and petrochemical hazardous waste provided by the present invention. Detailed Implementation

[0043] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0044] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0045] This invention provides a method for the resource-based treatment of gasification slag and petrochemical hazardous waste. Please refer to the following reference. Figure 1 In this embodiment, the method includes the following steps:

[0046] (1) The gasification slag is magnetically separated under the condition of an effective average magnetic field strength of 8000-14000G (i.e., Gauss) to obtain low magnetic slag.

[0047] (2) The petrochemical hazardous waste incineration ash, the low magnetic furnace slag and silicon-containing auxiliary materials are mixed, and the resulting mixture is melted at high temperature in an oxidizing atmosphere, then quenched and cooled to obtain a glass body, which is then crushed, ground, shaped and heat-treated to obtain microcrystalline glass.

[0048] Preferably, in the mixture, based on the total weight of the mixture, the content of SiO2 is 45-60 wt%, the content of Na2O is 12-19 wt%, the content of K2O is 0.5-2 wt%, the content of CaO is 4.5-10 wt%, the content of Al2O3 is 5.5-9.5 wt%, the content of Fe2O3 is 3.0-5.1 wt%, and the content of Cr2O3 is 0-0.58 wt%. Under the above conditions, the resulting microcrystalline glass has excellent performance, and the content of reddish-brown Fe2O3 is relatively low, making the microcrystalline glass more aesthetically pleasing and applicable to a wider range of scenarios. In this invention, Fe2O3 and Cr2O3 in the mixture act as nucleating agents in the preparation process of microcrystalline glass, while Na2O and K2O provide an alkaline environment for the system.

[0049] Gasification slag is a solid waste formed by the molten liquid phase of coal ash and additives under high-temperature conditions, along with residual carbon, after water quenching. The gasification slag contains substances such as Ni and its oxides, Co and its oxides, Fe, Fe2O3, Na2O, and K2O, with an Fe2O3 content of 15–23 wt%. If silicon-containing additives, petrochemical hazardous waste incineration ash, and gasification slag with high iron oxide content are directly mixed, the resulting mixture will contain many metallic impurities detrimental to the performance of the produced microcrystalline glass. Furthermore, a significant amount of silicon-containing additives and petrochemical hazardous waste incineration ash is required to obtain a mixture with an Fe2O3 content of 3.0–5.1%. Consequently, the amounts of Al2O3, K2O, and CaO in the mixture may be insufficient, necessitating the addition of corresponding additives, leading to higher costs and low utilization rates of the gasification slag and petrochemical hazardous waste incineration ash.

[0050] In this invention, by magnetically separating the gasification slag, some of the oxides and alloys of Fe, Co, and Ni, which are highly magnetic, are removed from the gasification slag. This reduces the impact of metallic impurities such as Co and Ni on the performance of the glass-ceramic, and the Fe2O3 in the low-magnetic slag is reduced to 5-12 wt%. Thus, based on the preparation of a mixture that meets the above requirements, the existing elements in the petrochemical hazardous waste incineration ash and gasification slag can be fully utilized without the need to add nucleating agents and alkaline substances (such as sodium carbonate, potassium carbonate, etc.), reducing the use of auxiliary materials and lowering the cost.

[0051] In a preferred embodiment, the specific process of magnetic separation includes: performing three-stage separation on the gasification slag, wherein the effective average magnetic field strength of the first-stage separation is 8000–9000 Gauss, the effective average magnetic field strength of the second-stage separation is 11000–12000 Gauss, and the effective average magnetic field strength of the third-stage separation is 12000–14000 Gauss. In the most preferred embodiment, the effective average magnetic field strengths of the three stages of separation are 8900, 11500, and 13000 Gauss, respectively.

[0052] Furthermore, the low-magnetic slag obtained from magnetic separation can be screened to obtain low-magnetic slag with an average particle size of less than 1 mm, which facilitates the subsequent high-temperature melting reaction.

[0053] In this invention, the gasification slag is selected from at least one of the waste residue discharged after quenching from a Texaco gasifier, a Shell gasifier, and an Orient gasifier (with coal-water slurry or pulverized coal feed). It is understood that the composition of gasification slag from different gasifiers varies, and it can be blended with different types of silicon-containing auxiliary materials and petrochemical hazardous waste incineration ash, depending on the specific selection of the gasification slag, to obtain a mixture that meets the above requirements.

[0054] In a specific embodiment, the silicon-containing auxiliary material is selected from at least one of silicon dioxide, quartz sand, and waste glass. To save costs, waste glass is preferred as the silicon-containing auxiliary material. More preferably, the average particle size of the silicon-containing auxiliary material is less than 1 mm. In practice, raw materials that meet the particle size requirements can be directly selected, or the selected raw materials can be crushed and sieved to meet the particle size requirements.

[0055] In this invention, the preparation process of the petrochemical hazardous waste incineration ash includes: mixing fly ash and bottom ash generated from the incineration of organic petrochemical hazardous waste, and crushing and sieving the resulting premixed ash. Preferably, sieving yields petrochemical incineration ash with an average particle size of less than 1 mm.

[0056] In a preferred embodiment, the pH of the leachate from the petrochemical hazardous waste incineration ash is 9-13.

[0057] This invention does not limit the specific types of organic petrochemical hazardous waste, and can be at least one of the following: typical petrochemical refining hazardous waste (hydrocarbon polymers from cracked filters, waste solvent oil, coke residue from cracked heat exchangers, waste fusel oil, etc.) and chemical hazardous waste (organic solvents).

[0058] In a preferred embodiment, the premixed ash is first purified, then crushed and sieved. The purification step includes: washing the obtained premixed ash with alkaline solution in a three-stage countercurrent manner to remove corrosive elements (such as F, Cl, etc.) from the organic petrochemical hazardous waste, so that the Cl content is less than 0.04 wt%. This avoids corrosion of the melting equipment by corrosive elements during high-temperature melting, extending the service life of the melting equipment. On the other hand, it ensures that the resulting microcrystalline glass meets the requirement of "granulated blast furnace slag powder for cement and concrete" (GB / T 18046-2017) for chloride ion content <0.06%, thus broadening the application scenarios of microcrystalline glass and further increasing its added value.

[0059] In this invention, the alkaline solution is selected from saturated sodium carbonate solution and / or saturated sodium bicarbonate solution.

[0060] In a specific embodiment, the weight ratio of the mixed ash residue to the alkaline solution is 4 to 10:1, for example, it can be 4:1, 5:1, 7:1, 9:1 or 10:1.

[0061] In a specific implementation, the operating temperature of the impurity removal step is 40–60°C.

[0062] To achieve better removal of corrosive elements, in this invention, the washing is performed 2 to 3 times, with each washing session lasting 5 to 10 minutes.

[0063] In this invention, based on the total weight of the petrochemical hazardous waste incineration ash, the content of SiO2 is 0.5–5 wt%, the content of Na2O is 45–60 wt%, the content of Al2O3 is 0–3.5 wt%, the content of total Fe2O3 is 2–4 wt%, and the content of CaO is 0.2–0.6 wt%. It should be noted that the above are the main components of the petrochemical hazardous waste incineration ash, and not all components.

[0064] It should be noted that, because the content of iron oxides in the petrochemical hazardous waste incineration ash is low, Fe was not distinguished during the detection process. 2+ and Fe 3+ The total Fe2O3 content here refers to the total amount of divalent iron oxides and trivalent iron oxides.

[0065] Furthermore, the hazardous characteristics of the petrochemical hazardous waste incineration ash residue are as follows: based on the total weight of the petrochemical hazardous waste incineration ash residue, the content of lead is <20mg / kg, mercury is <5mg / kg, arsenic is <50mg / kg, selenium is <30mg / kg, antimony is <10mg / kg, titanium is <800mg / kg, manganese is <500mg / kg, cobalt is <50mg / kg, barium is <800mg / kg, vanadium is <4000mg / kg, copper is <100mg / kg, zinc is <2500mg / kg, chromium is <4200mg / kg, nickel is <500mg / kg, cadmium is <5mg / kg, and cyanide is <5mg / kg. Therefore, the resulting microcrystalline glass exhibits excellent performance.

[0066] In a specific implementation, in step (2), the weight ratio of silicon dioxide in the petrochemical hazardous waste incineration ash, low magnetic furnace slag and silicon-containing auxiliary materials is 100:110-150:80-150. Specifically, for example, it can be 100:110:80, 100:110:110, 100:133:117, 100:140:120, 100:150:140 or 100:150:150.

[0067] In this invention, in step (2), the high-temperature melting step can have a melting temperature of 1300-1400°C and a melting time of 60-90 min.

[0068] In this invention, in step (2), the oxygen content in the oxidizing atmosphere can be 8-15%, preferably 8-12%.

[0069] In this invention, the flue gas generated during the high-temperature melting process contains heavy metal vapors and volatile components. Preferably, the kiln ash collected from the high-temperature flue gas generated during the high-temperature melting process is recovered and used to prepare petrochemical hazardous waste incineration ash, thereby reducing the emission of solid waste during resource recovery.

[0070] The quenching cooling can be water cooling, ice cooling, air cooling, or water quenching and ice cooling, etc. For ease of operation, water cooling or air cooling is adopted in this invention.

[0071] In a preferred embodiment, in step (2), the specific process of the heat treatment includes: first heating to 600-650°C and holding for 30-60 minutes, preferably 40-60 minutes, and then heating to 850-900°C and holding for 1-2 hours, preferably 1.5-2 hours.

[0072] More preferably, the heating rate of the first heating is 6-8°C / min.

[0073] More preferably, the heating rate of the second heating is 5 to 10 °C / min.

[0074] The present invention also proposes a microcrystalline glass, which is prepared by the method described above.

[0075] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0076] Example 1

[0077] (1) The fly ash and bottom ash produced by incineration of organic petrochemical hazardous waste were mixed. The resulting premixed ash (chlorine content 1.5 wt%) was then subjected to three-stage countercurrent washing twice with an alkaline solution (saturated sodium carbonate solution) at 40°C, each wash lasting 8 minutes. The weight ratio of the alkaline solution to the mixed ash was 1:5. The mixture was then crushed and sieved to obtain petrochemical hazardous waste incineration ash (chlorine content 0.03% wt%) with an average particle size less than 0.9 mm. The petrochemical hazardous waste incineration ash, based on its total weight, contained 2.0 wt% SiO2, 45 wt% Na2O, 1.7 wt% Al2O3, and a total Fe2+ content of 45 wt%. The content of O3 is 2.67 wt%, the content of CaO is 0.47 wt%, the content of lead is 18 mg / kg, the content of mercury is 4 mg / kg, the content of arsenic is 39 mg / kg, the content of selenium is 21 mg / kg, the content of antimony is 8 mg / kg, the content of titanium is 628 mg / kg, the content of manganese is 436 mg / kg, the content of cobalt is 47 mg / kg, the content of barium is 543 mg / kg, the content of vanadium is 3917 mg / kg, the content of copper is 78 mg / kg, the content of zinc is 2354 mg / kg, the content of chromium is 3806 mg / kg, the content of nickel is 412 mg / kg, the content of cadmium is 3 mg / kg, the content of cyanide is 1 mg / kg, and the pH of the leachate from the petrochemical hazardous waste incineration ash is 9.

[0078] (2) The gasification slag from the Dongfang furnace (Fe2O3 content of 21wt%) was subjected to three-stage separation. The effective average magnetic field strength of the first stage separation was 8900 Guass, the effective average magnetic field strength of the second stage separation was 11500 Guass, and the effective average magnetic field strength of the third stage separation was 13000 Guass, resulting in low magnetic slag with Fe2O3 content of 11wt%.

[0079] (3) The petrochemical hazardous waste incineration ash obtained in step (1), the low-magnetic furnace slag obtained in step (2), and the waste glass powder are mixed to obtain a mixture. The waste glass powder contains 70 wt% SiO2, and the weight ratio of petrochemical hazardous waste incineration ash, low-magnetic furnace slag, and waste glass powder (calculated as SiO2) is 100:110:80. The average particle size of both the low-magnetic furnace slag and the waste glass powder is less than 0.9 mm. The mixture contains, by weight percentage, approximately 50.5 wt% SiO2, approximately 14.9 wt% Na2O, and approximately 0.88 wt% K2O. The mixture contains approximately 7.39 wt% CaO, 6.35 wt% Al2O3, 4.55 wt% Fe2O3, and 0.44 wt% Cr2O3. The mixture is melted at 1300°C for 60 min in an oxidizing atmosphere (oxygen content 15%), then water-cooled to obtain a glass body. The glass body is crushed, ground, and extruded into shape. It is then heated to 600°C for the first time at a rate of 6°C / min and held for 60 min. The temperature is then raised to 850°C for the second time at a rate of 5°C / min and held for 2 h. After cooling, microcrystalline glass is obtained.

[0080] Example 2

[0081] (1) The fly ash and bottom ash produced by incineration of organic petrochemical hazardous waste were mixed. Under the condition of 40°C, the resulting premixed ash (chlorine content of 1.5 wt%) was washed twice with alkaline solution (saturated sodium carbonate solution) in a three-stage countercurrent manner, each time for 5 minutes. The weight ratio of alkaline solution to mixed ash was 1:4. Then, it was crushed and sieved to obtain petrochemical hazardous waste incineration ash (chlorine content of 0.04 wt%) with an average particle size of less than 1 mm. The petrochemical hazardous waste incineration ash contained, based on the total weight of the petrochemical hazardous waste incineration ash, 0.7 wt% SiO2, 60 wt% Na2O, 2.3 wt% Al2O3, and 0.5 wt% total Fe2O3. The content of 3 is 3.0 wt%, the content of CaO is 0.6 wt%, the content of lead is 13 mg / kg, the content of mercury is 2 mg / kg, the content of arsenic is 48 mg / kg, the content of selenium is 10 mg / kg, the content of antimony is 4 mg / kg, the content of titanium is 736 mg / kg, the content of manganese is 241 mg / kg, the content of cobalt is 12 mg / kg, the content of barium is 276 mg / kg, the content of vanadium is 3189 mg / kg, the content of copper is 93 mg / kg, the content of zinc is 1875 mg / kg, the content of chromium is 2904 mg / kg, the content of nickel is 469 mg / kg, the content of cadmium is 4 mg / kg, the content of cyanide is 3 mg / kg, and the pH of the leachate from the petrochemical hazardous waste incineration ash is 13.

[0082] (2) The gasification slag from the Shell furnace (Fe2O3 content of 17wt%) was subjected to three-stage separation. The effective average magnetic field strength of the first stage separation was 8900 Guass, the effective average magnetic field strength of the second stage separation was 11500 Guass, and the effective average magnetic field strength of the third stage separation was 12300 Guass, resulting in low magnetic slag with Fe2O3 content of 6wt%.

[0083] (3) The petrochemical hazardous waste incineration ash obtained in step (1), the low-magnetic furnace slag obtained in step (2), and the quartz sand are mixed to obtain a mixture. The weight ratio of the petrochemical hazardous waste incineration ash, the low-magnetic furnace slag, and the quartz sand (excluding SiO2 impurities) is 100:150:150. The average particle size of the low-magnetic furnace slag and the quartz sand is less than 1 mm. The mixture contains, by weight percentage, approximately 50 wt% SiO2, approximately 16.0 wt% Na2O, approximately 0.6 wt% K2O, and approximately 10 wt% CaO. The mixture contains approximately 6.7 wt% Al2O3, 3.0 wt% Fe2O3, and 0.35 wt% Cr2O3. The mixture is melted at 1400°C for 90 min in an oxidizing atmosphere (oxygen content 8%), then water-cooled to obtain a glass body. The glass body is crushed, ground, and extruded into shape. It is then heated to 650°C for the first time at a rate of 8°C / min and held for 60 min. The temperature is then raised to 900°C for the second time at a rate of 10°C / min and held for 1 h. After cooling, microcrystalline glass is obtained.

[0084] Example 3

[0085] (1) Fly ash and bottom ash generated from the incineration of organic petrochemical hazardous waste were mixed. The resulting premixed ash (chlorine content 2.1 wt%) was then subjected to three-stage countercurrent washing twice with an alkaline solution (saturated sodium bicarbonate solution) at 60°C, each wash lasting 10 minutes. The weight ratio of the alkaline solution to the mixed ash was 1:6. The mixture was then crushed and sieved to obtain petrochemical hazardous waste incineration ash with an average particle size less than 1 mm. The petrochemical hazardous waste incineration ash, based on its total weight, contained 1.2 wt% SiO2, 53 wt% Na2O, 0 wt% Al2O3, and 2.0 wt% total Fe2O3. The aO content is 0.31 wt%, lead content is 8 mg / kg, mercury content is 1 mg / kg, arsenic content is 23 mg / kg, selenium content is 29 mg / kg, antimony content is 7 mg / kg, titanium content is 652 mg / kg, manganese content is 481 mg / kg, cobalt content is 33 mg / kg, barium content is 384 mg / kg, vanadium content is 2743 mg / kg, copper content is 29 mg / kg, zinc content is 2148 mg / kg, chromium content is 4199 mg / kg, nickel content is 385 mg / kg, cadmium content is 4.5 mg / kg, cyanide content is 2 mg / kg, chlorine content is 0.05 wt%, and the pH of the leachate from the petrochemical hazardous waste incineration ash is 10.

[0086] (2) The gasification slag from the Dongfang furnace (Fe2O3 content of 15wt%) was subjected to three-stage separation. The effective average magnetic field strength of the first stage separation was 8000 Guass, the effective average magnetic field strength of the second stage separation was 11000 Guass, and the effective average magnetic field strength of the third stage separation was 12000 Guass, resulting in low magnetic slag with Fe2O3 content of 9.0wt%.

[0087] (3) The petrochemical hazardous waste incineration ash obtained in step (1), the low-magnetic furnace slag obtained in step (2), and the quartz sand are mixed to obtain a mixture. The weight ratio of the petrochemical hazardous waste incineration ash, the low-magnetic furnace slag, and the quartz sand (excluding SiO2 impurities) is 100:133:117. The average particle size of the low-magnetic furnace slag and the quartz sand is less than 1 mm. The mixture, by weight percentage, includes: approximately 60 wt% SiO2, approximately 12 wt% Na2O, approximately 2 wt% K2O, and approximately 4.62 wt% CaO. The mixture is prepared with approximately 5.5 wt% Al2O3, 3.99 wt% Fe2O3, and 0.58 wt% Cr2O3. The mixture is then melted at 1350°C for 90 min in an oxidizing atmosphere (oxygen content 8%), followed by water cooling to obtain a glass body. This glass body is then crushed, ground, and extruded. It is then heated to 630°C at a rate of 7°C / min and held for 50 min, followed by a second heating to 870°C at a rate of 10°C / min and held for 2 h. Finally, it is cooled to obtain microcrystalline glass.

[0088] Example 4

[0089] (1) Fly ash and bottom ash generated from the incineration of organic petrochemical hazardous waste were mixed. The resulting premixed ash (chlorine content 2.1 wt%) was then subjected to three countercurrent washings with an alkaline solution (saturated sodium bicarbonate solution) at 60°C, each washing lasting 10 minutes. The weight ratio of the alkaline solution to the mixed ash was 1:10. The mixture was then crushed and sieved to obtain petrochemical hazardous waste incineration ash with an average particle size of less than 1 mm. The petrochemical hazardous waste incineration ash, based on its total weight, contained 0.5 wt% SiO2, 50 wt% Na2O, 3.5 wt% Al2O3, and 4.0 wt% total Fe2O3. The content of CaO is 0.2 wt%, lead is 12 mg / kg, mercury is 4 mg / kg, arsenic is 49 mg / kg, selenium is 27 mg / kg, antimony is 2 mg / kg, titanium is 592 mg / kg, manganese is 341 mg / kg, cobalt is 28 mg / kg, barium is 644 mg / kg, vanadium is 3861 mg / kg, copper is 97 mg / kg, zinc is 2415 mg / kg, chromium is 0 mg / kg, nickel is 418 mg / kg, cadmium is 1.8 mg / kg, cyanide is 4.8 mg / kg, chlorine is 0.03 wt%, and the pH of the leachate from the petrochemical hazardous waste incineration ash is 11.

[0090] (2) The gasification slag from the Texaco furnace (Fe2O3 content of 16wt%) was subjected to three-stage sorting. The effective average magnetic field strength of the first-stage sorting was 9000 Guass, the effective average magnetic field strength of the second-stage sorting was 12000 Guass, and the effective average magnetic field strength of the third-stage sorting was 14000 Guass, resulting in low magnetic slag with Fe2O3 content of 11wt%.

[0091] (3) The petrochemical hazardous waste incineration ash obtained in step (1), the low-magnetic furnace slag obtained in step (2), and SiO2 are mixed to obtain a mixture. The average particle size of the low-magnetic furnace slag and SiO2 is less than 1 mm. The weight ratio of the petrochemical hazardous waste incineration ash, low-magnetic furnace slag, and SiO2 is 100:110:110. According to the test, the mixture contains, by weight percentage, approximately 45.5 wt% SiO2, approximately 18.7 wt% Na2O, approximately 0.56 wt% K2O, and approximately 9.6 wt% CaO. The mixture is composed of approximately 9.5 wt% Al2O3, approximately 5.0 wt% Fe2O3, and approximately 0 wt% Cr2O3. The mixture is melted at 1400°C for 70 min in an oxidizing atmosphere (oxygen content 12%), and then air-cooled to obtain a glass body. The glass body is crushed, ground, and extruded into shape. It is then heated to 650°C for the first time at a rate of 8°C / min and held for 40 min. It is then heated to 900°C for the second time at a rate of 7°C / min and held for 1.5 h. After cooling, microcrystalline glass is obtained.

[0092] Comparative Example 1

[0093] The method described in Example 1 is followed, except that no silicon-containing auxiliary material (i.e., waste glass powder) is added in step (3), and the resulting mixture contains, by weight percentage: approximately 31.9 wt% SiO2, approximately 20.6 wt% Na2O, approximately 1.22 wt% K2O, approximately 10.24 wt% CaO, approximately 8.80 wt% Al2O3, approximately 7.0 wt% Fe2O3, and approximately 0.61 wt% Cr2O3.

[0094] Comparative Example 2

[0095] The method described in Example 1 is followed, except that low-magnetic slag is not added in step (3). It is understood that step (2) is deleted accordingly, and the resulting mixture contains, by weight percentage: approximately 45.6 wt% SiO2, approximately 24.1 wt% Na2O, approximately 0.94 wt% K2O, approximately 2.6 wt% CaO, approximately 1.1 wt% Al2O3, approximately 1.25 wt% Fe2O3, and approximately 0.71 wt% Cr2O3.

[0096] Comparative Example 3

[0097] The method described in Example 1 is followed, except that the gasification slag is not subjected to a magnetic separation step and is directly mixed with petrochemical hazardous waste incineration ash, low-magnetic furnace slag and waste glass powder to obtain a mixture. The mixture, by weight percentage, includes: approximately 50.2 wt% SiO2, approximately 14.7 wt% Na2O, approximately 0.71 wt% K2O, approximately 7.21 wt% CaO, approximately 6.13 wt% Al2O3, approximately 7.95 wt% Fe2O3, and approximately 0.24 wt% Cr2O3.

[0098] Comparative Example 4

[0099] The method described in Example 1 is followed, except that only a glass body is produced, that is, the steps of crushing, grinding, extruding, and then heat-treating the glass body in step (3) are removed.

[0100] Test Example 1

[0101] The products obtained in Examples 1-4 and Comparative Examples 1-4 were subjected to physicochemical property tests. The test methods were carried out in accordance with JC / T 872. The test results are shown in Table 1 below.

[0102] Table 1

[0103]

[0104]

[0105] As can be seen from the results in Table 1, the microcrystalline glass prepared in Example 1 of this invention meets the standard of "JCT872-2019 Microcrystalline Glass for Architectural Decoration", indicating that the method provided by this invention can produce microcrystalline glass with excellent performance. Meanwhile, the Mohs hardness, flexural strength, and compressive strength of the product prepared in the comparative example are significantly lower than those of the example and do not meet the standard, indicating that this invention greatly improves the performance of microcrystalline glass through the design of raw materials, preparation steps, and related parameters.

[0106] Test Example 2

[0107] The heavy metal leaching amounts of the products obtained in Examples 1-4 were tested according to the standard methods corresponding to water leaching and acid leaching in GB / T 41015, and the results are shown in Table 2 below.

[0108] Table 2

[0109]

[0110]

[0111] As can be seen from Table 2, the microcrystalline glass prepared in the embodiments of the present invention has a low heavy metal leaching amount, which meets the requirements of the standard "Technical Requirements for Vitrification Products of Solid Waste" (GB / T 41015-2021) for "Limits of Hazardous Substance Content in Water Leaching and Acid Leaching of Vitrification Products". This shows that the method provided by the present invention can achieve the harmless treatment of petrochemical hazardous waste incineration ash and gasification slag.

[0112] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for the resource-based treatment of gasification slag and petrochemical hazardous waste, characterized in that, The method includes the following steps: (1) The gasification slag is magnetically separated under an effective average magnetic field strength of 8000~14000 G to obtain low magnetic slag; (2) The petrochemical hazardous waste incineration ash, the low magnetic furnace slag and silicon-containing auxiliary materials are mixed, and the resulting mixture is melted at high temperature in an oxidizing atmosphere, then quenched and cooled to obtain a glass body, which is then crushed, ground, shaped and heat-treated to obtain microcrystalline glass. In the mixture, based on the total weight of the mixture, the content of SiO2 is 45-60 wt%, the content of Na2O is 12-19 wt%, the content of K2O is 0.5-2 wt%, the content of CaO is 4.5-10 wt%, the content of Al2O3 is 5.5-9.5 wt%, the content of Fe2O3 is 3.0-5.1 wt%, and the content of Cr2O3 is 0-0.58 wt%. Based on the total weight of the petrochemical hazardous waste incineration ash, the content of SiO2 is 0.5~5 wt%, the content of Na2O is 45~60 wt%, the content of Al2O3 is 0~3.5 wt%, the content of total Fe2O3 is 2~4 wt%, and the content of CaO is 0.2~0.6 wt%.

2. The method according to claim 1, characterized in that, In step (1), the specific process of magnetic separation includes: performing three-stage separation on the gasification slag, with the effective average magnetic field strength of the first stage separation being 8000~9000 G, the effective average magnetic field strength of the second stage separation being 11000~12000 G, and the effective average magnetic field strength of the third stage separation being 12000~14000 G.

3. The method according to claim 1, characterized in that, The average particle size of the low-magnetic furnace slag is less than 1 mm.

4. The method according to claim 1, characterized in that, In step (1), the gasification slag is selected from at least one of the waste slag discharged after quenching from Texaco gasifier, Shell gasifier and Orient gasifier.

5. The method according to claim 1, characterized in that, In step (2), the silicon-containing auxiliary material is selected from at least one of silicon dioxide, quartz sand and waste glass; The average particle size of the silicon-containing auxiliary material is less than 1 mm.

6. The method according to claim 1, characterized in that, The preparation process of the petrochemical hazardous waste incineration ash residue includes: mixing fly ash and bottom ash generated from the incineration of organic petrochemical hazardous waste, and crushing and sieving the resulting premixed ash residue.

7. The method according to claim 1, characterized in that, The average particle size of the petrochemical hazardous waste incineration ash is less than 1 mm.

8. The method according to claim 1, characterized in that, The pH of the leachate from the petrochemical hazardous waste incineration ash residue is 9-13.

9. The method according to claim 6, characterized in that, The obtained premixed ash residue is first removed for impurities, then crushed and sieved. The impurity removal step includes: washing the obtained premixed ash residue with alkaline solution in three stages of countercurrent washing.

10. The method according to claim 9, characterized in that, The alkaline solution is selected from saturated sodium carbonate solution and / or saturated sodium bicarbonate solution.

11. The method according to claim 9, characterized in that, The weight ratio of the alkaline solution to the premixed ash is 1:4~10.

12. The method according to claim 9, characterized in that, The operating temperature for the impurity removal step is 40~60℃.

13. The method according to claim 9, characterized in that, The washing process is repeated 2 to 3 times, with each wash lasting 5 to 10 minutes.

14. The method according to claim 1, characterized in that, The hazardous characteristics of the petrochemical hazardous waste incineration ash residue are as follows, based on the total weight of the petrochemical hazardous waste incineration ash residue: lead content <20 mg / kg, mercury content <5 mg / kg, arsenic content <50 mg / kg, selenium content <30 mg / kg, antimony content <10 mg / kg, titanium content <800 mg / kg, manganese content <500 mg / kg, cobalt content <50 mg / kg, barium content <800 mg / kg, vanadium content <4000 mg / kg, copper content <100 mg / kg, zinc content <2500 mg / kg, chromium content <4200 mg / kg, nickel content <500 mg / kg, cadmium content <5 mg / kg, and cyanide content <5 mg / kg.

15. The method according to any one of claims 1-14, characterized in that, In step (2), the weight ratio of the petrochemical hazardous waste incineration ash, low magnetic furnace slag and silicon-containing auxiliary material is 100:110~150:80~150, wherein the silicon-containing auxiliary material is calculated by weight of SiO2.

16. The method according to any one of claims 1-14, characterized in that, In step (2), the high-temperature melting step has a melting temperature of 1300~1400℃ and a melting time of 60~90min.

17. The method according to any one of claims 1-14, characterized in that, The oxygen content in the oxidizing atmosphere is 8-15%.

18. The method according to claim 1, characterized in that, In step (2), the kiln ash collected from the high-temperature flue gas generated during the high-temperature melting process is recovered and used to prepare petrochemical hazardous waste incineration ash.

19. The method according to any one of claims 1-14, characterized in that, In step (2), the specific process of heat treatment includes: first heating to 600~650℃ and holding for 30~60min, and then heating to 850~900℃ and holding for 1~2h.

20. The method according to claim 19, characterized in that, The heating rate for the first heating is 6~8℃ / min.

21. The method according to claim 19, characterized in that, The heating rate for the second heating is 5~10℃ / min.

22. A microcrystalline glass, characterized in that, Prepared by the method according to any one of claims 1-21.

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